Synthesis and investigations of novel alkenylporphyrins and bis(porphyrins)

Twelve porphyrin dyads linked by an ethene bridge were synthesised as model systems for conjugated polymers. The extent of interporphyrin interaction was investigated for meso-meso and meso-β linked homo- and heterobimetallo-porphyrin dyads. To complement these dyads, model monomers with alkenyl substituents were also studied. Once the synthesis of these compounds was achieved, the extent of interaction was studied using UV-visible and fluorescence spectroscopy and molecular modelling. In order to gain a true indication of the extent of interaction in a dyad, the effect of the bridge as a substituent must be accounted for. This was achieved by studying the series of monomers by UV-visible and fluorescence spectroscopy. The increased conjugation resulting from mono- and bis-alkenyl substituents results in a red shift of the origin of transition energies in the absorption spectrum which is accompanied by a broadened and less intense Soret band and an increase in the intensity of the Q bands. The emission of these compounds also displays an increase in Stokes shift and a loss of vibronic coupling due to the increased conjugation. The serendipitous synthesis of three asymmetric meso-β ethene-linked porphyrin dyads was achieved by the use of palladium-catalysed Heck coupling of mesoethenyl- with meso-bromoporphyrins. A possible mechanism for this meso to β rearrangement was proposed. A series of nine meso-meso ethene-linked dyads was synthesised by palladium-catalysed Suzuki coupling of meso-(2-iodoethenyl)- with meso-borolanylporphyrins. All of these dyads were characterised by 1D and 2D NMR as well as MS analysis. The absorption spectra of ethene-linked dyads exhibit a split Soret band and a red-shifted and intensified HOMO-LUMO band. In the meso-β dyads, the degree of splitting in the Soret band is sufficient only to generate a shoulder on the red edge, whereas in the meso-meso dyads two separate bands appear. The extent of splitting is believed to be an indication of the amount of porphyrin-porphyrin interaction. The fluorescence profiles of the dyads change dramatically depending upon the central substituents in the porphyrins and the wavelength used for irradiation, which suggests that different conformations of these compounds give rise to different parts of their absorption and emission profiles. The fluorescence profiles of the dyads also do not reflect their absorption profiles, and therefore the excitation of the dyad is believed to be accompanied also by a change in geometry. All ethene-linked dyads exhibited an anti-Stokes shift, and the excitation spectra of the different parts of the fluorescence envelope also support the possibility of different conformers contributing to the fluorescence spectra. Molecular mechanics and time-dependent quantum mechanical calculations were performed on seven ethene-linked porphyrin dyads. These calculations further support the proposal of different conformations contributing to the physical properties of ethene-linked dyads. Electronic structure calculations also show considerable electron density on the alkene for the meso-meso ethene-linked dyads, which highlights the important influence of this bridge upon the electronic nature of these conjugated diporphyrins

The Heck reaction for porphyrin functionalisation: synthesis of meso-alkenyl monoporphyrins and palladium-catalysed formation of unprecedented meso-β ethene-linked diporphyrins

Palladium-catalysed coupling of the vinyl derivatives methyl acrylate, styrene and acrylonitrile with 5-bromo-10,15,20-triphenylporphyrin (MTriPPBr; M = 2H, Ni, Zn) and 5,15-dibromo-10,20-bis(3,5-di-tert-butylphenyl)porphyrin (MDAPBr2) produced a series of mono- and disubstituted alkenylporphyrins, thus demonstrating the applicability of meso-haloporphyrins in Heck-type reactions. The same technique was also applied to meso-ethenylporphyrins and simple aryl halides, with mixed results. Only meso-vinyl nickel(II) porphyrins showed any reactivity under our conditions. A mixture of 1,1- and 1,2-disubstitution across the alkene was observed for 5-vinyl-10,15,20-triphenylporphyrinatonickel(II) (meso-vinylNiTriPP), whereas 5-vinyl-10,20-bis(3,5-di-t-butylphenyl)porphyrinatonickel(II) (meso-vinylNiDAP) produced a mixture of meso-1,1-, meso-1,2- and, surprisingly, β-1,2-disubstituted Heck products. Coupling meso-vinylNiDAP with MTriPPBr under similar Heck conditions led unexpectedly to trans β-meso-NiDAP-ethene-MTriPP dyads, affording the first members of a new class of alkenyl-linked diporphyrins. A mechanism for the unusual meso to β rearrangement is discussed. The electronic absorption spectra of the dyads have a red-shifted shoulder on the Soret (B) band, which is evidence of a moderate degree of electronic interaction between the porphyrins via the ethenyl bridge

Meso-iodo- and Meso-iodovinylporphyrins Via Organo-Palladium Porphyrins and The Crystal Structure of 5-iodo-10,20-Diphenylporphyrin

The regiospecific halogen exchange reactions of various easily accessible meso-bromoporphyrins to obtain meso-iodoporphyrins, using η1-palladioporphyrins as intermediates, have been investigated. This one-pot methodology allows the isolation of meso-iodoporphyrins in excellent yields with short reaction times. Similarly meso-(2-bromoethenyl)porphyrins can be converted to their iodoethenyl analogues. These iodoporphyrins show great potential as starting materials for various palladium catalysed reactions. The X-ray crystal structure of 5-iodo-10,20-diphenylporphyrin has been determined

Meso-Iodo- and meso-iodovinylporphyrins via organopalladium porphyrins and the crystal structure of 5-iodo-10,20-diphenylporphyrin

The regiospecific halogen exchange reactions of various easily accessible meso-bromoporphyrins to obtain meso-iodoporphyrins, using η1-palladioporphyrins as intermediates, have been investigated. This one-pot methodology allows the isolation of meso-iodoporphyrins in excellent yields with short reaction times. Similarly meso-(2-bromoethenyl)porphyrins can be converted to their iodoethenyl analogues. These iodoporphyrins show great potential as starting materials for various palladium catalysed reactions. The X-ray crystal structure of 5-iodo-10,20-diphenylporphyrin has been determined

Infrared Spectroscopic Study of Potassium and Cesium Acetate-Intercalated Kaolinites

Near-IR spectroscopy has been used to elucidate the structure of potassium and cesium acetate-intercalated kaolinites. Three near-IR spectral regions are identified: (a) the high frequency region between 6400 and 7400 cm−1 attributed to the first overtone of the hydroxyl stretching mode, (b) the 4800–5400 cm−1 region attributed to water combination modes and (c) the 4000–4800 cm−1 region attributed to the combination of the stretching and deformation modes of the AlOH units of kaolinite. The technique of near-IR spectroscopy for the study of intercalated kaolinites shows great potential for the understanding of the interactions between the surface hydroxyls of kaolinite and the inserting potassium and acetate ions. In particular, whereas the overlap of the hydroxyl stretching frequencies of water and the kaolinite overlap in the mid-IR, such overlap does not occur in the near-IR. In the first overtone region, a single sharp band is observed at 7045 cm−1 which is assigned to the combination of the hydroxyl stretching frequencies of the inner surface hydroxyls and water. Such an observation supports the concept of an interaction between the water and the inner surface hydroxyls of the intercalated kaolinite. It is suggested that the bonding of the acetate to the kaolinite hydroxyls is through the water molecule

Near-Infrared and Mid-Infrared Spectroscopic Study of Sepiolites and Palygorskites

Near-IR spectroscopy has been used to distinguish between palygorskites and sepiolites. Three near-IR spectral regions contain bands due to (a) the high frequency region between 6400 and 7400 cm−1 attributed to the first overtone of the hydroxyl stretching mode, (b) the 4800–5400 cm−1 region attributed to water combination modes and (c) the 4000–4800 cm−1 region attributed to the combination of the stretching and deformation modes of the M–MgOH units of palygorskites and sepiolites. Near-IR bands are observed in the first region and are assigned to the first overtone of the hydroxyl stretching frequency observed at 3620 and 3410 cm−1 in the mid-IR spectra. The near-IR bands observed in the second region are assigned to the combination of the water OH stretching and deformation vibrational modes. A complex set of low intensity bands are observed in the 4100–4600 cm−1 region and are attributed to the combination of the cation hydroxyl stretching, deformation and translation modes. The difference between the near-IR spectra of palygorskites and sepiolites depends on the dioctahedral nature of the palygorskites and the trioctahedral structure of the sepiolites. Changes in the near-IR spectra are therefore related to the Mg3(OH) and Mg2(OH) units in the palygorskites

Homo- and heteronuclear meso,meso-(E)-ethene-1,2-diyl-linked diporphyrins: Preparation, x-ray crystal structure, electronic absorption and emission spectra and density functional theory calculations

Homo-and heteronuclear meso,meso-(E)-ethene-1,2-diyl-linked diporphyrins have been prepared by the Suzuki coupling of porphyrinylboronates and iodovinylporphyrins. Combinations comprising 5,10,15-triphenylporphyrin (TriPP) on both ends of the ethene-1,2-diyl bridge M 210 (M 2=H 2/Ni, Ni 2, Ni/Zn, H 4, H 2Zn, Zn 2) and 5,15-bis(3,5-di-tert-butylphenyl)porphyrinato-nickel(II) on one end and H 2, Ni, and ZnTriPP on the other (M 211), enable the first studies of this class of compounds possessing intrinsic polarity. The compounds were characterized by electronic absorption and steady state emission spectra, 1H NMR spectra, and for the Ni 2 bis(TriPP) complex Ni 210, single crystal X-ray structure determination. The crystal structure shows ruffled distortions of the porphyrin rings, typical of Ni II porphyrins, and the (E)-C 2H 2 bridge makes a dihedral angle of 50° with the mean planes of the macrocycles. The result is a stepped parallel arrangement of the porphyrin rings. The dihedral angles in the solid state reflect the interplay of steric and electronic effects of the bridge on interporphyrin communication. The emission spectra in particular, suggest energy transfer across the bridge is fast in conformations in which the bridge is nearly coplanar with the rings. Comparisons of the fluorescence behaviour of H 410 and H 2Ni10 show strong quenching of the free base fluorescence when the complex is excited at the lower energy component of the Soret band, a feature associated in the literature with more planar conformations. TDDFT calculations on the gas-phase optimized geometry of Ni 210 reproduce the features of the experimental electronic absorption spectrum within 0.1 eV. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Experimental and Theoretical Characterization of 5,10-Diminoporphodimethenes: Dearomatized Porphyrinoids from Palladium-Catalyzed Hydrazinations of 5,10- Diarylporphyrins

A new dearomatized porphyrinoid, 5,10-diiminoporphodimethene (5,10-DIPD), has been prepared by palladium-catalyzed hydrazination of 5,10-dibromo-15,20-bis(3,5-di-tert-butylphenyl)porphyrin and its nickel(II) complex, by using ethyl and 4-methoxybenzyl carbazates. The oxidative dearomatization of the porphyrin ring occurs in high yield. Further oxidation with 2,3-dichloro-5,6-dicyanobenzoquinone forms the corresponding 5,10-bis(azocarboxylates), thereby restoring the porphyrin aromaticity. The UV/visible spectra of the NiII DIPDs exhibit remarkable redshifts of the lowest-energy bands to 780 nm, and differential pulse voltammetry reveals a contracted electrochemical HOMO–LUMO gap of 1.44 V. Density functional theory (DFT) was used to calculate the optimized geometries and frontier molecular orbitals of model 5,10-DIPD Ni7c and 5,10-bis(azocarboxylate) Ni8c. The conformations of the carbamate groups and the configurations of the C[DOUBLE BOND]N[BOND]Z unit were considered in conjunction with the NOESY spectra, to generate the global minimum geometry and two other structures with slightly higher energies.In the absence of solution data regarding conformations, ten possible local minimum conformations were considered for Ni8c. Partition of the porphyrin macrocycle into tri- and monopyrrole fragments in Ni7c and the inclusion of terminal conjugating functional groups generate unique frontier molecular orbital distributions and a HOMO–LUMO transition with a strong element of charge transfer from the monopyrrole ring. Time-dependent DFT calculations were performed for the three lowest-energy structures of Ni7c and Ni8c, and weighting according to their energies allowed the prediction of the electronic spectra. The calculations reproduce the lower-energy regions of the spectra and the overall forms of the spectra with high accuracy, but agreement is not as good in the Soret region below 450 nm